CN106475103B - A kind of preparation method of methane portion oxidation synthesis gas catalyst - Google Patents
A kind of preparation method of methane portion oxidation synthesis gas catalyst Download PDFInfo
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- CN106475103B CN106475103B CN201610003101.3A CN201610003101A CN106475103B CN 106475103 B CN106475103 B CN 106475103B CN 201610003101 A CN201610003101 A CN 201610003101A CN 106475103 B CN106475103 B CN 106475103B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 43
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 47
- 239000001257 hydrogen Substances 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 229920003169 water-soluble polymer Polymers 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- QDMGKUOANLJICG-UHFFFAOYSA-N [Mg].[N+](=O)(O)[O-] Chemical compound [Mg].[N+](=O)(O)[O-] QDMGKUOANLJICG-UHFFFAOYSA-N 0.000 claims 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- -1 polyethylene Polymers 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 238000001914 filtration Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000003643 water by type Substances 0.000 description 21
- 230000004913 activation Effects 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- LBPYPRXFFYUUSI-UHFFFAOYSA-N furan-2-carbaldehyde;hydrate Chemical compound O.O=CC1=CC=CO1 LBPYPRXFFYUUSI-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method of methane portion oxidation synthesis gas catalyst, the catalyst includes active component, auxiliary agent and carrier, and the preparation method of the catalyst includes the following steps：Catalyst precarsor B is prepared first, then reduction treatment is carried out to catalyst precarsor B, it is uniformly mixed with furfural aqueous solution by auxiliary agent presoma is soluble in water, then it is added in autoclave with together with catalyst precarsor B, it is reacted after solution D is added, filtering obtained solid sample obtains catalyst again after drying, calcination process after obtained solidliquid mixture processing separation.Catalyst reaction activity prepared by this method is high, not only reduces metal consumption, but also the hot spot during methane portion oxidation is inhibited to generate.
Description
Technical field
The present invention relates to a kind of preparation methods of methane portion oxidation synthesis gas catalyst, more particularly, to a kind of methane
The preparation method of portion oxidation synthesis gas loaded catalyst.
Background technology
90% or more of gas component is methane, is natural gas profit by methane through synthesis gas synthetic fuel and chemicals again
One of effective way.With traditional vapour reforming ratio, methane portion oxidation synthesis gas has required reaction vessel body
The synthesis gas that the small, reaction rate of product is fast, low energy consumption and generates is suitable as the advantages that unstripped gas of methanol and Fiscber-Tropscb synthesis.Separately
Outside, exploitation methane portion oxidation technology is possible to replace highly endothermic methane steam reformation technique for producing synthesis gas, special
It is not to be of great significance for remote or offshore natural gas resource utilization.
The main catalyst system of methane portion oxidation synthesis gas is by active component noble metal（Pt, Pd, Rh, Ru,
Ir）, nickel or cobalt be supported on the carriers such as aluminium oxide, silica, magnesia, zirconium oxide, titanium oxide, while can be used alkali metal,
Alkaline-earth metal or rare-earth oxide are modified to improve the reactivity worth of catalyst.
CN 101049566A disclose a kind of for the Ni bases catalyst of methane portion oxidation synthesis gas and its preparation side
Method.The carrier of catalyst is complex carrier Mg-Al-Ce-Zr-O, active component NiO.The patent is made using coprecipitation method
Obtained carrier is dipped in Ni (NO by complex carrier3)2In solution, methane conversion reaches 84% or more, CO on obtained catalyst
Selectivity reaches 99% or more.
CN 101219393A disclose a kind of cobalt-based loaded catalyst for methane portion oxidation synthesis gas and its
Preparation method.Catalyst takes step impregnation method to prepare, and is to help with a kind of alkaline-earth metal or rare earth metal using Co as active component
Agent, using HZSM-5 as carrier, catalyst activity obtained is high, coking resistivity is strong, stability is good.
CN 101284241A disclose a kind of catalyst of methane portion oxidation synthesis gas and preparation method thereof.With mistake
It is active component that metal Co, which is crossed, with noble metal, using a kind of element selected from alkaline-earth metal as auxiliary agent, with γ-Al2O3For carrier, adopt
The catalyst of methane portion oxidation synthesis gas is made with infusion process.Catalyst has high activity, excellent coking resistivity, Gao Wen
Qualitative advantage.
Although catalyst made from above-mentioned patented method obtains preferable methane portion oxidation synthesis gas reactivity
Can, but since the reaction is a fast reaction（This fast reaction, which is typically at, to be carried out under conditions of mass transport limitation）,
Reactant reacts while reaching catalyst external surface to be completed, thus the inner surface of catalyst contributes not goal response
Greatly, this has resulted in lower rate of metal in carrier duct, while can also accelerate the deep oxidation of product.
Invention content
To overcome shortcoming in the prior art, the present invention provides a kind of methane portion oxidation synthesis gas catalyst
Preparation method, catalyst prepared by this method has the characteristics that of low cost, metal component utilization rate is high and selectively good.
The present invention provides a kind of preparation method of methane portion oxidation synthesis gas catalyst, the catalyst includes living
Property component, auxiliary agent and carrier, active component Ni, one or more of auxiliary agent Ca, Mg, Zr, Ce or La, carrier be oxidation
Any one of aluminium, silica；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, active component
Content is 10wt%~25wt%, preferably 10wt%~20wt%, and the content of auxiliary agent is 1wt%~5wt%, preferably 3wt%~5wt%, remaining
Amount is carrier；The preparation method of the catalyst includes the following steps：
（1）Active component presoma is soluble in water, obtain solution A；
（2）Carrier is added to step（1）In obtained solution A, after dipping, aging, drying, calcination process, obtain
Catalyst precarsor B；
（3）Using reducing atmosphere to step（2）Obtained catalyst precarsor B carries out reduction treatment；
（4）Auxiliary agent presoma is soluble in water, obtain solution C, and be uniformly mixed with furfural aqueous solution, then with step
（3）Obtained catalyst precarsor B is added in autoclave together；
（5）High molecular weight water soluble polymer, active component presoma is soluble in water, obtain solution D；Solution D is added
To step（4）It in the autoclave, is replaced 2~5 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 2~4MPa,
1~3h is reacted at 100~200 DEG C；
（6）Wait for step（5）Obtained solidliquid mixture is down to 20~30 DEG C, and absolute ethyl alcohol or aqueous citric acid solution is added,
1~2h is placed, is then filtered, obtained solid sample after drying, calcination process, obtains catalyst again.
In the preparation method of methane portion oxidation synthesis gas catalyst of the present invention, step（1）Described in before active component
Drive body is nickel nitrate, nickel acetate, nickel sulfate, one or more in nickel chloride, preferably nickel nitrate；In the solution A, activity
Based on the element, mass fraction in the solution is 1%~7% to component.
In the preparation method of methane portion oxidation synthesis gas catalyst of the present invention, step（2）Described in dipping be etc.
Volume impregnation, dip time are 1~3h；The aging can aging at room temperature, can also aging at a constant temperature, always
Change temperature be 10~90 DEG C, preferably 20~60 DEG C, ageing time be 1~for 24 hours, preferably 4~12h；Step（2）With step
（6）Described in drying temperature be 70~150 DEG C, preferably 80~120 DEG C, drying time be 2~12h, preferably 4~8h；Step
Suddenly（2）With step（6）Described in calcination temperature be 500~900 DEG C, preferably 600~800 DEG C, roasting time be 2~12h, it is excellent
It is selected as 4~8h.
In the preparation method of methane portion oxidation synthesis gas catalyst of the present invention, step（2）Described in carrier be oxygen
Change any one of aluminium, silica, commercially available product may be used in the carrier, can also be by method system well known in the art
It is standby；In the catalyst precarsor B, the nickel of load is 1wt%~5wt% of final catalyst in terms of element wt.
In the preparation method of methane portion oxidation synthesis gas catalyst of the present invention, step（3）Described in reducing atmosphere
For the mixed gas of hydrogen or hydrogen and nitrogen, hydrogen volume content is 10%~95% in the mixed gas.It is specific to go back
Former processing procedure is as follows：Catalyst precarsor B is warming up to 300~600 DEG C under nitrogen atmosphere, then passes to hydrogen or hydrogen and nitrogen
The mixed gas of gas, in 0.1~0.5MPa（Absolute pressure）After handling 4~8h, it is down to room temperature in a nitrogen atmosphere.
In the preparation method of methane portion oxidation synthesis gas catalyst of the present invention, step（4）Described in auxiliary agent forerunner
Body is calcium nitrate, calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, one or more in lanthanum nitrate,
Preferably magnesium nitrate；In the solution C, based on the element, mass fraction in the solution is 1%~4% to auxiliary agent；The furfural is water-soluble
The mass fraction of furfural is 30%~50% in liquid；Step（4）Described in furfural aqueous solution and the mass ratio of solution C be 3~5, institute
State solution C and the gross mass and step of furfuryl aldehyde solution（3）The mass ratio of obtained reduction rear catalyst precursor B is 3~6.
In the preparation method of methane portion oxidation synthesis gas catalyst of the present invention, step（5）Described in water-soluble high score
Sub- polymer is polyethylene glycol（PEG）, polyvinylpyrrolidone（PVP）, polyvinyl alcohol（PVA）One or more of；It is described
Active component presoma is nickel nitrate, nickel acetate, nickel sulfate, one or more in nickel chloride, preferably nickel nitrate；It is described molten
In liquid D, in active component presoma the nickeliferous mass fraction in solution D based on the element be 0.4%~2%, water-soluble high score
Mass fraction of the sub- polymer in solution D is 3~6 times of Ni element mass fractions.
In the preparation method of methane portion oxidation synthesis gas catalyst of the present invention, step（6）Described in anhydrous second is added
The mass ratio of the quality and high molecular weight water soluble polymer of alcohol or citric acid is 2~4；The mass fraction of the aqueous citric acid solution
It is 10%~20%.
Catalyst prepared by the method for the present invention can be applied to methane portion oxidation synthesis gas reaction.Catalyst is using
It is preceding in a hydrogen atmosphere, 700~800 DEG C of 1~3h of prereduction.Catalyst prepared by the method for the present invention is applied to methane portion oxidation
Preparing synthetic gas reacts, and preferable process conditions are：The composition CH of unstripped gas4/O2Molar ratio is 1.75~2.2, can be in unstripped gas
Contain Ar, N2Or the dilution property gas such as He, 20000~200000h of unstripped gas air speed-1, reaction pressure is 0.1~1Mpa, reaction
Temperature is 600~900 DEG C.
Compared with prior art, the preparation method being related to through the invention can obtain a kind of distribution of active metal outer layer
Methane portion oxidation synthesis gas nickel-base catalyst.In the present invention, pre-soaked a part of active metal is to carry out furfural water
Phase hydrogenation reaction.Active metal predecessor and high molecular weight water soluble polymer, a side is added simultaneously in the system of furfural hydrogenation
Face hinders active metal to the diffusion inside catalyst granules using furfural hydrogenation product；On the other hand, before using active metal
The coordination between object and high molecular weight water soluble polymer is driven, active metallic ion is inside and outside catalyst granules in reduction solution
Concentration difference, slow down active metal to the diffusion velocity inside catalyst granules.Catalyst reaction activity prepared by this method is high,
Not only metal consumption is reduced, but also the hot spot during methane portion oxidation is inhibited to generate.Catalyst precarsor is handled and is urged simultaneously
Agent prepares a step and completes, and preparation process is simple, is conducive to industrial amplification.
Specific implementation mode
The technology contents and effect further illustrated the present invention with reference to embodiment, but it is not so limited the present invention.
Evaluation condition：With hydrogen reducing 2 hours at 700 DEG C before catalyst reaction of the present invention.In continuous sample introduction fixed bed
It is reacted in quartz reactor, 750 DEG C of reaction temperature, unstripped gas forms CH4/O2/Ar = 2/1/4（Molar ratio）, air speed 1 ×
105h-1, gas-chromatography on-line analysis is used after the condensed water removal of product.Sampling analysis after reaction 1 hour, evaluation results are shown in Table 1.
The metal element content in catalyst is determined using XRF analysis technology.Using scanning electron microscope analysis institute of the present invention
The distribution situation of active component on a catalyst in the catalyst of preparation.Catalyst activity obtained by the embodiment of the present invention and comparative example
The scanning electron microscope analysis of component nickel the results are shown in Table 2.
Embodiment 1
It weighs 2.97g nickel nitrates to be dissolved in 13mL deionized waters, obtains solution A；It is carried on using equi-volume impregnating
14.9g alumina supports（Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm）, soak at room temperature
Stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, obtained catalyst precarsor B, the Ni of load are in terms of element wt, for most
The 3% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；8.55g magnesium nitrates are dissolved in 16mL deionized waters, are obtained
Solution C, and with the mass fraction of its 4 times of quality be 40% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；10.8g polyethylene glycol, 11.89g nickel nitrates are dissolved in 200mL deionized waters
In, obtain solution D；Solution D is also added in autoclave, is replaced 3 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure
To 3MPa, 2h is reacted at 150 DEG C；Solidliquid mixture after being reacted in above-mentioned autoclave is down to 25 DEG C, and the anhydrous second of 33g is added
Alcohol is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, that is, makes
It is 12.6%Ni to obtain quality based on the element and account for catalyst percentage composition, and the catalyst of 3.7%Mg is denoted as C-1.
Embodiment 2
It weighs 2.97g nickel nitrates to be dissolved in 12mL deionized waters, obtains solution A；It is carried on using equi-volume impregnating
14.9g silica supports（Kong Rongwei 0.97mL/g, specific surface area 372m2/ g, spherical, equivalent diameter 0.5mm）, soak at room temperature
Stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, obtained catalyst precarsor B, the Ni of load are in terms of element wt, for most
The 3% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；8.55g magnesium nitrates are dissolved in 16mL deionized waters, are obtained
Solution C, and with the mass fraction of its 4 times of quality be 40% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；10.8g polyethylene glycol, 11.89g nickel nitrates are dissolved in 200mL deionized waters
In, obtain solution D；Solution D is also added in autoclave, is replaced 3 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure
To 3MPa, 2h is reacted at 150 DEG C；Solidliquid mixture after being reacted in above-mentioned autoclave is down to 25 DEG C, and the anhydrous second of 33g is added
Alcohol is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, that is, makes
It is 11.8%Ni to obtain quality based on the element and account for catalyst percentage composition, and the catalyst of 3.1%Mg is denoted as C-2.
Embodiment 3
It weighs 0.99g nickel nitrates to be dissolved in 15mL deionized waters, obtains solution A；It is carried on using equi-volume impregnating
16.5g alumina supports（Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm）, soak at room temperature
Stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, obtained catalyst precarsor B, the Ni of load are in terms of element wt, for most
The 1% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；6.41g magnesium nitrates are dissolved in 16mL deionized waters, are obtained
Solution C, and with the mass fraction of its 4 times of quality be 40% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；8.1g polyethylene glycol, 8.92g nickel nitrates are dissolved in 200mL deionized waters,
Obtain solution D；Solution D is also added in autoclave, after sealing with hydrogen replace 3 times, then adjust Hydrogen Vapor Pressure to
3MPa reacts 2h at 150 DEG C；Solidliquid mixture after being reacted in above-mentioned autoclave is down to 25 DEG C, and the anhydrous second of 25g is added
Alcohol is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, that is, makes
It is 8.7%Ni to obtain quality based on the element and account for catalyst percentage composition, and the catalyst of 2.2%Mg is denoted as C-3.
Embodiment 4
It weighs 4.96g nickel nitrates to be dissolved in 11mL deionized waters, obtains solution A；It is carried on using equi-volume impregnating
13.3g alumina supports（Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm）, soak at room temperature
Stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, obtained catalyst precarsor B, the Ni of load are in terms of element wt, for most
The 5% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；10.68g magnesium nitrates are dissolved in 16mL deionized waters, are obtained
Solution C, and with the mass fraction of its 4 times of quality be 40% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；13.5g polyethylene glycol, 14.87g nickel nitrates are dissolved in 200mL deionized waters
In, obtain solution D；Solution D is also added in autoclave, is replaced 3 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure
To 3MPa, 2h is reacted at 150 DEG C；Solidliquid mixture after being reacted in above-mentioned autoclave is down to 25 DEG C, and the anhydrous second of 41g is added
Alcohol is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, that is, makes
It is 17.3%Ni to obtain quality based on the element and account for catalyst percentage composition, and the catalyst of 4.1%Mg is denoted as C-4.
Embodiment 5
It weighs 2.97g nickel nitrates to be dissolved in 13mL deionized waters, obtains solution A；It is carried on using equi-volume impregnating
14.9g alumina supports（Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm）, soak at room temperature
Stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, obtained catalyst precarsor B, the Ni of load are in terms of element wt, for most
The 3% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；3.77g zirconium nitrates are dissolved in 16mL deionized waters, are obtained
Solution C, and with the mass fraction of its 4 times of quality be 40% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；10.8g polyethylene glycol, 11.89g nickel nitrates are dissolved in 200mL deionized waters
In, obtain solution D；Solution D is also added in autoclave, is replaced 3 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure
To 3MPa, 2h is reacted at 150 DEG C；Solidliquid mixture after being reacted in above-mentioned autoclave is down to 25 DEG C, and the anhydrous second of 33g is added
Alcohol is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, that is, makes
It is 12.1%Ni to obtain quality based on the element and account for catalyst percentage composition, and the catalyst of 3.2%Zr is denoted as C-5.
Embodiment 6
It weighs 2.97g nickel nitrates to be dissolved in 13mL deionized waters, obtains solution A；It is carried on using equi-volume impregnating
14.9g alumina supports（Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm）, soak at room temperature
Stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, obtained catalyst precarsor B, the Ni of load are in terms of element wt, for most
The 3% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；4.72g calcium nitrate is dissolved in 16mL deionized waters, is obtained
Solution C, and with the mass fraction of its 3 times of quality be 30% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；By 10.8g polyvinylpyrrolidones（k30）, 11.89g nickel nitrates are dissolved in
In 200mL deionized waters, solution D is obtained；Solution D is also added in autoclave, after sealing with hydrogen replace 3 times, so
Hydrogen Vapor Pressure is adjusted afterwards to 3MPa, reacts 2h at 150 DEG C；Solidliquid mixture after being reacted in above-mentioned autoclave is down to 25
DEG C, the aqueous citric acid solution that 220g mass fractions are 15% is added, places 1.5h, then filters, obtained solid sample is put into baking oven
In at 110 DEG C dry 6h, roast 6h at 700 DEG C, it is 13.1%Ni to obtain quality based on the element and account for catalyst percentage composition,
The catalyst of 3.5%Ca, is denoted as C-6.
Embodiment 7
It weighs 2.97g nickel nitrates to be dissolved in 13mL deionized waters, obtains solution A；It is carried on using equi-volume impregnating
14.9g alumina supports（Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm）, soak at room temperature
Stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, obtained catalyst precarsor B, the Ni of load are in terms of element wt, for most
The 3% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；2.48g lanthanum nitrates are dissolved in 16mL deionized waters, are obtained
Solution C, and with the mass fraction of its 5 times of quality be 50% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；10.8g polyvinyl alcohol, 11.89g nickel nitrates are dissolved in 200mL deionized waters
In, obtain solution D；Solution D is also added in autoclave, is replaced 3 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure
To 3MPa, 2h is reacted at 150 DEG C；Solidliquid mixture after being reacted in above-mentioned autoclave is down to 25 DEG C, and the anhydrous second of 33g is added
Alcohol is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, that is, makes
It is 12.6%Ni to obtain quality based on the element and account for catalyst percentage composition, and the catalyst of 3.7%La is denoted as C-7.
Comparative example
It weighs 14.86g nickel nitrates and 8.55g magnesium nitrates is dissolved in deionized water, aqueous solution is made；Using incipient impregnation
Method is carried on 16.2g alumina supports（Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm）,
Impregnate 2h at room temperature, aging 6h, 110 DEG C of dry 6h, 700 DEG C of roasting 6h obtain quality based on the element and account for catalyst percentage and contain
Amount is 14.7%Ni, and the catalyst of 3.6%Mg is denoted as D-1.
The reactivity worth of 1 catalyst of table
2 catalyst activity component Ni content distributions of table（wt%）
Claims (24)
1. a kind of preparation method of methane portion oxidation synthesis gas catalyst, the catalyst include active component, auxiliary agent and
Carrier, active component Ni, one or more of auxiliary agent Ca, Mg, Zr, Ce or La, carrier are in aluminium oxide, silica
It is any；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, the content of active component be 10wt%~
The content of 25wt%, auxiliary agent are 1wt%~5wt%, and surplus is carrier；The preparation method of the catalyst includes the following steps：
（1）Active component presoma is soluble in water, obtain solution A；
（2）Carrier is added to step（1）In obtained solution A, after dipping, aging, drying, calcination process, it is catalyzed
Agent precursor B；
（3）Using reducing atmosphere to step（2）Obtained catalyst precarsor B carries out reduction treatment；
（4）Auxiliary agent presoma is soluble in water, obtain solution C, and be uniformly mixed with furfural aqueous solution, then with step（3）
To catalyst precarsor B be added in autoclave together；
（5）High molecular weight water soluble polymer, active component presoma is soluble in water, obtain solution D；Solution D is added to step
Suddenly（4）It in the autoclave, is replaced 2~5 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 2~4MPa,
1~3h is reacted at 100~200 DEG C, the high molecular weight water soluble polymer is polyethylene glycol, polyvinylpyrrolidone, polyethylene
One or more of alcohol；
（6）Wait for step（5）Obtained solidliquid mixture is down to 20~30 DEG C, and absolute ethyl alcohol or aqueous citric acid solution is then added,
1~2h is placed, is then filtered, obtained solid sample after drying, calcination process, obtains catalyst again.
2. according to the method for claim 1, it is characterised in that：The hundred of catalyst quality is accounted for each element quality in catalyst
Divide on the basis of ratio, the content of active component is 10wt%~20wt%, and the content of auxiliary agent is 3wt%~5wt%.
3. according to the method for claim 1, it is characterised in that：Step（1）Described in active component presoma be nickel nitrate,
It is one or more in nickel acetate, nickel sulfate, nickel chloride.
4. according to the method described in claim 1 or 3, it is characterised in that：Step（1）Described in active component presoma be nitric acid
Nickel.
5. according to the method for claim 1, it is characterised in that：Step（1）Described in solution A, active component is with element
Meter, the mass fraction in solution A are 1%~7%.
6. according to the method for claim 1, it is characterised in that：Step（2）Described in catalyst precarsor B, the nickel of load
It is 1wt%~5wt% of final catalyst in terms of element wt.
7. according to the method for claim 1, it is characterised in that：Step（2）Described in dipping be incipient impregnation, dipping
Time is 1~3h.
8. according to the method for claim 1, it is characterised in that：Step（2）Described in aging temperature be 10~90 DEG C, always
Change the time be 1~for 24 hours.
9. according to the method described in claim 1 or 8, it is characterised in that：Step（2）Described in aging temperature be 20~60
DEG C, ageing time is 4~12h.
10. according to the method for claim 1, it is characterised in that：Step（2）With step（6）Described in drying temperature be 70
~150 DEG C, drying time is 2~12h.
11. according to the method described in claim 1 or 10, it is characterised in that：Step（2）With step（6）Described in drying temperature
It it is 80~120 DEG C, drying time is 4~8h.
12. according to the method for claim 1, it is characterised in that：Step（2）With step（6）Described in calcination temperature be 500
~900 DEG C, roasting time is 2~12h.
13. according to the method described in claim 1 or 12, it is characterised in that：Step（2）With step（6）Described in calcination temperature
It it is 600~800 DEG C, roasting time is 4~8h.
14. according to the method for claim 1, it is characterised in that：Step（3）Described in reducing atmosphere be hydrogen or hydrogen
The mixed gas of gas and nitrogen, hydrogen volume content is 10%~95% in the mixed gas.
15. according to the method for claim 1, it is characterised in that：Step（4）Described in auxiliary agent presoma be calcium nitrate,
It is one or more in calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, lanthanum nitrate.
16. according to the method described in claim 1 or 15, it is characterised in that：Step（4）Described in auxiliary agent presoma be nitric acid
Magnesium.
17. according to the method for claim 1, it is characterised in that：Step（4）Described in solution C, auxiliary agent based on the element,
Mass fraction in solution C is 1%~4%.
18. according to the method for claim 1, it is characterised in that：Step（4）Described in furfural aqueous solution furfural quality
Score is 30%~50%.
19. according to the method for claim 1, it is characterised in that：Step（4）Described in furfural aqueous solution and solution C matter
Amount is than being 3~5.
20. according to the method for claim 1, it is characterised in that：Step（4）Described in solution C and furfural aqueous solution it is total
Quality and step（3）The mass ratio of obtained reduction rear catalyst precursor B is 3~6.
21. according to the method for claim 1, it is characterised in that：Step（5）Described in active component presoma be nitric acid
It is one or more in nickel, nickel acetate, nickel sulfate, nickel chloride.
22. according to the method described in claims 1 or 21, it is characterised in that：Step（5）Described in active component presoma be nitre
Sour nickel.
23. according to the method for claim 1, it is characterised in that：Step（5）Described in solution D, active component presoma
Middle the nickeliferous mass fraction in solution D based on the element is 0.4%~2%, matter of the high molecular weight water soluble polymer in solution D
Measure 3~6 times that score is Ni element mass fractions.
24. according to the method for claim 1, it is characterised in that：Step（6）Described in absolute ethyl alcohol or citric acid is added
The mass ratio of quality and high molecular weight water soluble polymer is 2~4；The mass fraction of the aqueous citric acid solution is 10%~20%.
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